CN105061690B - A kind of preparation method of high water reducing type solid high-performance polycarboxylate water-reducer - Google Patents
A kind of preparation method of high water reducing type solid high-performance polycarboxylate water-reducer Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of high water reducing type solid high-performance polycarboxylate water-reducer, comprise the following steps that：After the unsaturated APEO combination polymeric monomer heating melting of two kinds of different molecular weights, the mixed liquor of unsaturated carboxylic acid class minor comonomer, unsaturated acyl amine minor comonomer and chain-transferring agent is added dropwise under initiator effect, it is made by free radical bulk polymerization, used after the completion of reaction nertralizer adjust pH for 5~6, after cooling by grinding be solid granular.Present invention process is simple, high conversion rate and it is environment friendly and pollution-free the advantages of, the characteristics of using high diminishing, low-dosage in concrete and dry powder and mortar greatly reduces cost of transportation in long-distance transport.
Description
Technical field
The present invention relates to the technical field of concrete admixture, a kind of high property of high water reducing type solid polycarboxylic acids is related specifically to
The preparation method of energy water reducer.
Background technology
The synthesis of traditional poly carboxylic acid series water reducer is to be formed in aqueous by radical polymerization, mother liquor product solid content
40% or so, this causes very big Cost Problems to long-distance transportation, is needed in dry powder and mortar before use by liquid water reducer
Product carries out spray drying rear and can be used, but drying process with atomizing process high energy consumption, and diminishing agent molecule has in pyroprocess
Constituent reduction is imitated, performance does not reach the water-reducing rate of liquid polycarboxylate water-reducer in actual applications.
Patent CN103012694A reports a kind of preparation method of the pure solid high-performance polycarboxylate water-reducer of polyester-type.Should
Patent is using (methyl) acrylic monomers and polyethylene glycols as reaction monomers, the generation esterification polymeric monomer under catalyst action,
It is made with unsaturated carboxylic acid monomer by free radical bulk polymerization.Prepared by the invention two-step method, complex process, and esterification effect
Rate influences big to late phase reaction, it is difficult to form large-scale production.
Patent CN102993387A reports a kind of method that a step directly synthesizes pure solid high-performance polycarboxylate water-reducer.
The patent carries out the reaction of one-step method free radical bulk copolymerization with acrylic compounds and unsaturated APEO and is prepared from
Pure solid polycarboxylic acid water reducing agent, the invention uses a kind of molecule without heat drying or the separation postprocessing working procedures such as solvent
The solid high-performance polycarboxylate water-reducer of the unsaturated APEO synthesis of amount still can not meet wanting for high diminishing low-dosage
Ask.
The polycarboxylate water-reducer of pure solid will not only possess the high water-reducing property of conventional solution polycarboxylate water-reducer, Er Qieyao
Realize that technique simplifies, the production requirement of environmental protection.
The content of the invention
It is high there is provided a kind of high water reducing type solid polycarboxylic acids the invention aims to improve the deficiencies in the prior art
The preparation method of performance water reducer, the high water reducing type solid polycarboxylic acids synthesized under without any solvent environment using mass polymerization
High-performance water reducing agent, the water-reducing rate to improve ready-mixed concrete.
The technical scheme is that：A kind of preparation method of high water reducing type solid high-performance polycarboxylate water-reducer, specifically
Step is as follows：The combination of unsaturated APEO the polymeric monomer A and B of two kinds of different molecular weights are placed in kettle, after heating melting,
Initiator is added, then begins to be added dropwise the mixing of unsaturated carboxylic acid class minor comonomer, unsaturated acyl amine minor comonomer and chain-transferring agent
Liquid, time for adding is 2~8h, is incubated 1.5~3h in melting temperature after being added dropwise to complete, is completed by free radical bulk polymerization
Use afterwards nertralizer adjust pH for 5~6, after cooling by grinding be solid granular；Wherein described unsaturated APEO
A, unsaturated APEO B, unsaturated carboxylic acid acids minor comonomer, unsaturated acyl amine minor comonomer, initiator, chain-transferring agent and
The mass ratio of nertralizer is 1：(0.08~0.25)：(0.13~0.25)：(0.01~0.02)：(0.005~0.01)：(0.01
~0.015)：(0.01~0.015).
It is preferred that above-mentioned unsaturated APEO polymeric monomer A is methyl allyl alcohol polyoxyethylene ether, isobutene alcohol polyoxy
Vinethene or isoamyl alcohol polyoxyethylene ether；Molecular weight is 2400~5000；Described unsaturated APEO polymeric monomer B is
Methoxy poly (ethylene glycol) monomethyl ether acrylate or methyl allyl alcohol polyoxyethylene ether；Molecular weight is 800~1400；
It is preferred that above-mentioned unsaturated carboxylic acid class minor comonomer is at least one of acrylic or methacrylic acid.
It is preferred that above-mentioned unsaturated acyl amine minor comonomer is acrylamide, NMA or N-isopropylacrylamide
At least one of.
It is preferred that above-mentioned initiator is in azodiisobutyronitrile, ABVN, benzoyl peroxide or ammonium persulfate
At least one.
It is preferred that above-mentioned chain-transferring agent is at least one of TGA, 2 mercaptopropionic acid or sodium hypophosphite.
It is preferred that above-mentioned nertralizer is at least one of sodium hydroxide, calcium hydroxide, magnesium hydroxide or triethanolamine.
It is preferred that heating melting temperature is 55 DEG C~85 DEG C.
Beneficial effect：
1. a kind of preparation method of high water reducing type high performance water reducing agent of polyocarboxy acid of the present invention is using mass polymerization synthesis,
The polycarboxylate water-reducer of preparation is pure solid product, and high conversion rate, water-reducing rate height, volume are low, stable storing, and greatly drop
Low cost of transportation.
2. the present invention is using polyether macromonomer copolymerization in without any solvent of different side chain lengths, by space steric effect
Stereochemical structure is formd, peptizaiton of the water reducer in cement granules is effectively improved.
Embodiment
Technical solution of the present invention is further described below by embodiment.
Embodiment 1
100g methyl allyl alcohol polyoxyethylene ethers (molecular weight is 2400) and 25g methyl allyl alcohol polyoxyethylene ethers (are divided
Son amount is heated to after 55 DEG C of meltings 1400) to be placed in kettle, adds 0.5g azodiisobutyronitriles, then begins to that 13g propylene is added dropwise
The mixed liquor of acid, 1g acrylamides and 1g TGAs, time for adding is 2, is incubated 3h after being added dropwise to complete at 55 DEG C, and reaction is completed
It is 5.5 to add 1g sodium hydroxides adjustment pH afterwards, by grinding is solid granular after cooling.
Embodiment 2
By 100g isobutene alcohols APEO (molecular weight is 2900) and 20g methyl allyl alcohol polyoxyethylene ether (molecules
Measure 1200) to be placed in kettle, be heated to after 65 DEG C of meltings, add 0.6g ABVNs, then begin to that 15g propylene is added dropwise
The mixed liquor of acid, 1.3g NMAs and 1.2g mercaptopropionic acids, time for adding is 3, in 65 DEG C of insulations after being added dropwise to complete
2h, it is 5 that 1.2g calcium hydroxides adjustment pH is added after the completion of reaction, by grinding is solid granular after cooling.
Embodiment 3
By 400g isoamyl alcohol polyoxyethylene ethers (molecular weight is 3500) and 60g methoxy poly (ethylene glycol) monomethyl ether acrylic acid
Ester (molecular weight is 800) is placed in kettle, is heated to after 60 DEG C of meltings, is added 3.2g ammonium persulfates, then begins to that 72g methyl is added dropwise
The mixed liquor of acrylic acid, 6g N-isopropylacrylamides and 5.2g sodium hypophosphites, time for adding is 5, at 60 DEG C after being added dropwise to complete
1.5h is incubated, it is 5.3 that 5.2g magnesium hydroxides adjustment pH is added after the completion of reaction, by grinding is solid granular after cooling.
Embodiment 4
By 300g isobutene alcohols APEO (molecular weight is 5000) and 24g (0.08) methoxy poly (ethylene glycol) monomethyl ether
Acrylate (molecular weight is 1200) is placed in kettle, is heated to after 70 DEG C of meltings, is added 2.1g azodiisobutyronitriles, then begin to
The mixed liquor of 69g methacrylic acids, 5.4g acrylamides and 4.2g sodium hypophosphites is added dropwise, time for adding is 6, after being added dropwise to complete
2h are incubated at 70 DEG C, it is 6 that 4.2g triethanolamines adjustment pH is added after the completion of reaction, by grinding are solid granular after cooling.
Embodiment 5
By 360g methyl allyl alcohol polyoxyethylene ethers (molecular weight is 2900) and 36g (0.1) methallyl alcohol polyoxyethylene
Ether (molecular weight is 1400) is placed in kettle, is heated to after 85 DEG C of meltings, is added 3.6g benzoyl peroxides, then begins to be added dropwise
The mixed liquor of 90g methacrylic acids, 7.2g NMAs and 5.4g2- mercaptopropionic acids, time for adding is 8, is added dropwise to complete
1.5h are incubated at 85 DEG C afterwards, it is 5.5 that 5.4g calcium hydroxides adjustment pH is added after the completion of reaction, by grinding are solid after cooling
It is granular.
1. flowing degree of net paste of cement is tested
Experiment is with reference to GB8077-2000《Methods for testing uniformity of concrete admixture》, W/C=0.29, in identical volume
Under paste flowing degree of each embodiment in reference cement is tested.From existing commercially available performance preferably liquid high-performance
Polycarboxylate water-reducer (reference examples) is as a comparison sample.Result of the test is shown in Table 1
The pulp flowage results of property of table 1
From table 1 it follows that the high water reducing type solid polycarboxylic acid water reducing agent contrast high property of liquid of the inventive method synthesis
Energy poly carboxylic acid series water reducer, has excellent net slurry dispersive property in solid volume 0.15%.
2. testing concrete performance
Experiment is with reference to GB8076-2008《Concrete admixture》To sample obtained by embodiment and commercially available performance preferably liquid
High-performance polycarboxylic acids water reducing agent (reference examples) carries out concrete strength inspection.Solid volume of the sample in cement is 0.28%,
From reference cement, cement on the basis of concrete mix：Sand：Stone：Water=360:812:1033:195.Result of the test is shown in Table 2
The concrete slump of table 2, divergence and compression strength
From Table 2, it can be seen that high water reducing type solid poly carboxylic acid series water reducer prepared by the inventive method, under low-dosage
Excellent diminishing dispersive property is shown in concrete compared with liquid high-performance polycarboxylic acids water reducing agent.
Claims (7)
1. a kind of preparation method of high water reducing type solid high-performance polycarboxylate water-reducer, it is comprised the following steps that：By two kinds of differences
The combination of unsaturated APEO the polymeric monomer A and B of molecular weight are placed in kettle, after heating melting, are added initiator, are then begun to
The mixed liquor of unsaturated carboxylic acid class minor comonomer, unsaturated acyl amine minor comonomer and chain-transferring agent is added dropwise, time for adding is 2~8h,
1.5~3h is incubated after being added dropwise to complete under melting temperature, by being adjusted after the completion of free radical bulk polymerization using nertralizer
PH be 5~6, after cooling by grinding be solid granular；Wherein described unsaturated APEO A, unsaturated polyoxyethylene
Ether B, unsaturated carboxylic acid acids minor comonomer, unsaturated acyl amine minor comonomer, initiator, the mass ratio of chain-transferring agent and nertralizer are
1：(0.08~0.25)：(0.13~0.25)：(0.01~0.02)：(0.005~0.01)：(0.01~0.015)：(0.01~
0.015)；Wherein described unsaturated APEO polymeric monomer A is methyl allyl alcohol polyoxyethylene ether, isobutene alcohol polyoxy second
Alkene ether or isoamyl alcohol polyoxyethylene ether；Molecular weight is 2400~5000；Described unsaturated APEO polymeric monomer B is first
Epoxide monomethyl polyethylene glycol acrylate ester or methyl allyl alcohol polyoxyethylene ether；Molecular weight is 800~1400.
2. preparation method according to claim 1, it is characterised in that described unsaturated carboxylic acid class minor comonomer is acrylic acid
At least one of or methacrylic acid.
3. preparation method according to claim 1, it is characterised in that described unsaturated acyl amine minor comonomer is acryloyl
At least one of amine, NMA or N-isopropylacrylamide.
4. preparation method according to claim 1, it is characterised in that described initiator is azodiisobutyronitrile, azo two
At least one of different heptonitrile, benzoyl peroxide or ammonium persulfate.
5. preparation method according to claim 1, it is characterised in that described chain-transferring agent is TGA, 2- sulfydryls third
At least one of acid or sodium hypophosphite.
6. preparation method according to claim 1, it is characterised in that described nertralizer be sodium hydroxide, calcium hydroxide,
At least one of magnesium hydroxide or triethanolamine.
7. preparation method according to claim 1, it is characterised in that the temperature of heating melting is 55 DEG C~85 DEG C.
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| CN109928661A (en) * | 2019-04-15 | 2019-06-25 | 山西格瑞特建筑科技股份有限公司 | A kind of viscosity reduction type solid polycarboxylic acid water reducing agent and preparation method thereof |
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| CN115340640A (en) * | 2021-05-12 | 2022-11-15 | 南京博特新材料有限公司 | Preparation method of viscosity-reduction type solid polycarboxylate superplasticizer |
| CN113603839A (en) * | 2021-08-27 | 2021-11-05 | 贵州凯襄新材料有限公司 | Composite polycarboxylic acid water reducing agent and preparation method and application thereof |
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